2-[vinyl-dicarboxylic acid ester]-3-amino-1, 2, 4-triazoles and process of preparing the same



Patented July 19, 1949 I 2,476,549

Z-[VINYL-DICARBOXYLIC ACID as'rnm-s- AMINB- LZL-TRIAZOLES AND PROCESS OFR ERAJENQ TH? SAME .zNew eo'r eim acl iianfl Walter K lly, Jr., Binhamton, Y., as's ignors to General Aniline 8a.- =Film Gorporation, NewYork, N. Y., a corporafiend-"Delaware" 1310, l l rarty-in gj. Qapplication Octohfil'. 22,

I 1945i, al N N Q.f1, 934. Divided and this apgember 7, 1946, Serial No.714,906-

' semi-m (Cl. 260-308) l his invention relates to g-tymykdicarhoxylicwherein R is an alkyl group,". g1 methyl, ethyl, acid ester]-3-amino-l,2,fl triazoles, and to a propyl, butyl, and the like, and 'Riishydrogen or method of preparing the same. an alkyl group of thesamevalue as R.

It is known in the art that light-sensitive emul- The method for thepreparation of 2-. [vinylsions, such as gelatin silver-halide emulsions;dicarboxylic acid ester]-3-amino-l,2,4 trlazoles have a decidedtendeney-to fog. The fee maybe consists of condensing 1 mol of analkoxymethyl of two types',namely,'yellow' fog and-ichemieal ene malonicester, of the following general for- (gray) fog. The yellow sometimesreferred mula:

to as color fog or dichroic fog is essentially a colloidal deposit ofsilver, the eglpr-intensi-ty and 6; I

general a a n e o hisk. are term d by the minute particle size anddegreeoffsubdivision, ,9011

The fog' ischiefly yellow in "color and is most apparent in the lighterportions of a negative. Wherem,R2'1S 0i m9SameVa1ue 3 .3 Wl i 9. 1 Thecolor .hbweverj wealth? colloidal of 3-am1no-1,2,4-tr1azoleof thefollowing-general silver 'partieles may, for example, appear greenformula:

by reflected light, jai ye low or redby, trans: EINJTQX. mitted light."The so-called cnenucal, or gray M m o n other andle e mor calamari andis formed in a'number of'wvays. It maybe caused by pr a su y ex e i rien wherein R3 is of the same value as R1.

h 61111115191151 b 2 .fi 'fi fi 9 111m PM Suitable alkoxyrnethylenemalonic esters are, 3 at h 1? mee atm s 9? 141 55 3 for example, methylmethoxymethylene malonate, T P ethyl methoxymethylene malonate, methyleth- 5 an oblect Q fi WVQPPP? t9 r .roxymethylene malonate, ethylethoxymethylene Vida z'winyl'dicarboxyfic acid ew-amin malonate, propylethoxymethylene malonate, 1,2,4-triazoles useful as stabilizers forsilver-halide ethyl yj ma d iat flmj emulsionstoxymethylene malonate,and the like v Another 1 1 1 of hi :iWQilflPfl-E- g l' As suitable 3-amino-1,2,4-triazoles may be a process o p ee n EYmL d bQ i mentioned,3-arnino 1,- 2,4-triaiole, 3-a m ino-5 acid ester] m oslfifiq riazmes.methyl-1,2,4-triazole, 3@amintFS ethyl 1,2,4 -trl- A er b i to IPWQQ 2-1inY -diw azole,3-amino-5-propyl-1,2,4-triazo1e, 3-amino-5- boxylic ciest r :em 9 l3A-fifl 9 as isoprooyl-1,2,4-triazole,and the-like.stabilizersor fog inhibiting gen prevent the ,formation of sensitivesheer-halide em A still further object 1 Q m hght" malonic ester and the3-amino -l ,2,4 triaz ole is I1 carried. out by allowing the reactioncomponents 9 z z t 2F to stand at room temperature: with occasionaldwarboxyhc a i es at- -.aminQ- 2 shaking, in the presences? an alcoh olw ater as stabilizers or anti-fogging agents f Sensitive t'l temulsi'qnshwhich do 40 days. The product either'pre'cipitates, or isrelower the sensltlvttyf*the"emu1s1n' and Wmch moved by evaporation ofthe solvent mixture at room temperature.

The final product is recrystallized from either alcohol or boilingwater. During the-condensation reaction the hydrogen atom on thesecondary 7 a o en o t r azo a koxyerouplof; malortlc ester i l z thealkoxymethylene malonic ester split outwith resulting condensationproduct is characterlzed the formation of an alcohoL r by a Structure 9the rim-mowing Asexamplesof suitable alcohols, which maybe generalformul used as solvents for the condensationireaction oooR inrecrystallizing the final product, may be -m a 1101, isopropyl alcohol,and the lilfe. The a1koxymethylene .malonic '--3-amino-1,2,4-triazo1eare we} t h h n to The condensationbetweenfthe alkoxymethylene blightmixture. for a p i doitign ranging from 1 th -"3- tione d, methylalcohol, ethyl alcoholgpropyl al'co;.

and the method for their preparation need not be described herein.

Specific compounds which have been prepared in accordance with the aboveprocedures, with their formulas, are as follows:

(1) C O C2H5 O O C2Hs l \CH HzN- =N 2- [B,B-dicarbethoxyvinyl]-3-amin01,2,4triazole =CH N-N 2- [fi,fi-dicarbethoxyvinyl]-3-amino-5methyl-1,2,4-trlazole C 0 0 on.

=CNN l 0 0 CH CH H2N- =N/ 2- B,B-dicarbomethoxyvinyl]-3-amino-1,2,4-tris.zole C 0 0 CH =CH NN ('JOOCHS CCa 7 2-B,B-dicarbomethoxyvinyl] -3-amino-5-propyl-1,2,4- triazole The followingexamples are intended to illustrate the preparation of the compoundsdisclosed above. It will be appreciated that the condi tions ofreactions, e. g., time of reaction and temperature, may be varied, andthat the supplementary process of purification may be resorted towherever found desirable.

Example I 0 0 02m C=OH-V--NN coocim \CH 2- Bfidicarbethoxyvinyl3-amino-5-methyl-1,2,4-triaz0le To a mixture of cc. of ethanol and 3 cc.of water, 0.05 mol (4.9 grams) of 3-amino-5-methyl- 1,2,4-triazole and0.05 mol (10.8 grams) of ethyl ethoxymethylene malonate were added andthe mixture allowed to stand at room temperature for 2 days. The solventof the reaction mixture was evaporated off at room temperature and theproduct dissolved in ethanol, filtered, and recrystallized from ethanol.

Example III 0 o 0 on.

=CH N-N ('30 O CH; l CH HzN- =N 2- [B,B-dicarbomethoxyvinyl]-3-amino-1,2,4-triazole To a mixture of 20 cc. of ethanol and 5 cc. ofwater, 0.05 mol (4.2 grams) of 3-amino-1,2,4- triazole and 0.05 mol (9.4grams) of methyl ethoxymethylene malonate were added and the mixtureallowed to stand at room temperature for 1 day. The white product whichslowly crystallized out was filtered, washed with ether, andrecrystallized from boiling Water.

'In the preparation of emulsions containing the stabilizers as aboveprepared, a solution of the stabilizer in a suitable solvent, such asalcohol or analcohol-water mixture, adjusted to a neutral or slightlyalkaline pH, i. e., pH 7.5 to 10, is made up and the solution mixed withthe emulsion at any point during its preparation, but preferably duringripening or just prior to coating in concentrations varying from 25 mg.to 500 mg. per liter of emulsion. The actual concentration employed willdepend upon the type of emulsion used, and may vary somewhat with theparticular compound employed. 7

The method of testing the stabilizers employed in the following examplesconsists of coating two film strips, such as cellulose acetate, with thesame emulsion, one with and one without stabilizer, storing theemulsionsin an incubator for six days at 50 0., then exposing,developing, fixing, and Washing the same under standard conditions. Thefog density or blackening produced in the unexposed areas in the twoemulsions is then measured in a transmission densitometer of standardtype.

The following examples will serve to illustrate certain Ways in whichthe 2-[vinyl-dicarboxylic acid ester]-3-amino-1,2,4-triazoles, of ourinven tion, are applied as stabilizers for silver-halide emulsions, butare not to be construed as limiting the invention.

Example IV A photographic film coated with an ordinarygelatin-bromoiodide emulsion of normal speed and contrast on developmentunder standard conditions, after incubation for six days at 50 0., gavea fog of 0.28 density. Another film coated with the same emulsioncontaining an addition of mg. of the compound of Example I per 1000 cc.of emulsion, equivalent to about 50 grams of silver-halide, anddeveloped under the same conditions, after the same incubation, gave afog of only 0.06 density.

Example V Example IV was repeated with the exception that an equivalentquantity of the compound of Example II was substituted for the compoundof Example I. The results obtained were almost identical with thoseobtained in Example IV.

Example VI Example IV was again repeated with the exception that 75 mgs.of the compound of Example III were substituted for 100 mgs. of thecompound of Example I. After incubation and development, the emulsioncontaining the compound of Example III gave a fog of only 0.1.

Further experiments have shown that emulsions containing stabilizers inaccordance with our invention have not only improved keeping qualities(i. e., a reduction in the fog produced by incubation or by longstorage), but in addition do not effect changes in speed to which someemulsions are susceptible.

The stabilizers which we have prepared and employed may be used invarious kinds of emulsions. In addition to being useful inorthochromatic and panchromatic emulsions, they may also be employed innon-sensitized emulsions and X-ray emulsions. If used with sensitizingdyes they may be added to the emulsion before or after the dyes areadded. The dispersin agents for the silver-halides may be gelatin orother colloid such as water-soluble cellulose derivatives, e. g.,hydroxy ethyl cellulose, methyl cellulose, carboxy-oxy-cellulose, lowacetyl value cellulose acetate, and the like. The stabilizers may alsobe employed in gelatin or other colloid, such as polyamides or a mixtureof gelatin with a polyamide as described in United States Patent2,289,775; polyvinyl alcohol and jelling compound as described in UnitedStates Patent 2,249,537; polyvinyl acetaldehyde acetal resins andpartially hydrolyzed acetate resins described in United States Patents1,939,422 and 2,036,092; cellulose derivatives, e. g., cellulosenitrate, cellulose acetate, the lower fatty acid esters of celluloseincluding simple and mixed esters, ethers of cellulose, and the like, asan overcoat for the emulsion, or as a backing layer for the support.Moreover, they may be incorporated in the support for the sensitiveemulsion layer or in an intermediate layer between the sensitiveemulsion layer and the support, such as the baryta coating commonly usedin photographic papers. Again, the otherwise finished photographicmaterial may be bathed in an alcohol or alcohol-water solutioncontaining the stabilizer.

This application is a division of our co-pending application Serial No,704,934, filed on October 22, 1946, now U. S, Patent 2,449,226.

Various modifications of this invention will occur to persons skilled inthe art and it is, therefore, understood that the patent granted shallonly be limited by the appended claims.

We claim:

1. A chemical compound of the general formula:

H2Ni=N wherein R is an alkyl group of not more than four carbon atoms,and R1 is a member selected from the class consisting of hydrogen and analkyl group of not more than four carbon atoms.

2. A chemical compound corresponding to the formula:

O=CH N-N to 001m \OH 3. A chemical compound corresponding to theformula:

4. A chemical compound corresponding to the formula:

5. The process of producing 2- [vinyl-dicarboXylic acid ester] 3 amino1,2,4 triazoles, which comprises treating 1 mol of a compound of thegeneral formula:

( 0 0R: C=CH-OR2 (E O 0 R2 with 1 mol of the general formula:

HNN

HzN- =N wherein R2 is an alkyl group of not more than four carbon atomsand R3 is a member selected from the class consisting of hydrogen and analkyl group of not more than four carbon atoms in the presence of analcohol-Water mixture at room temperature, for a period of time rangingfrom 1 to 3 days.

6. The process which comprises treating 1 mol of ethyl ethoxymethylenemalonate with 1 mol of 3-amino-1,2,4-triazole in the presence of analcohol-water mixture at room temperature, for a period of time rangingfrom 1 to 3 days.

7. The process which comprises treating 1 mol of ethyl ethoxymethylenemalonate with 1 mol of 3-amino-5-methyl-1,2,4-'triazole in the presenceof an alcohol-water mixture at room temperature, for a period of timeranging from 1 to 3 days.

8. The process which comprises treating 1 mol of methyl ethoxymethylenemalonate with 1 mol of 3-amino-1,2,4-triazo1e in the presence of analcohol-water mixture at room temperature, for a period of time rangingfrom 1 to 3 days.

NEWTON HEIMBACH. WALTER KELLY, JR.

REFERENCES CITED UNITED STATES PATENTS Name Date Brodersen Mar. 4, 1941Number

